Effect of Surface Curvature on Colloidal Stability of Silver Nanoparticles with Monomolecular and Mixed Thiol Ligand Layers in the Presence of Alkali Cations.

Colloidal stability of silver nanoparticles is the critical parameter while designing colloidal colorimetric biosensors. Here, we examined colloidal stability of 11-mercaptoundecanoate-capped quasi-spherical silver nanoparticles and silver nanoplates in 0.02 M phosphate buffers with pH 8.0 containing Li+ , Na+ , K+ , or Cs+ cations. While quasi-spherical nanoparticles demonstrate a good colloidal stability in the presence of all studied cations, nanoplates aggregate in the presence of Na-phosphate buffer. The mechanism of aggregation consists in the ion-specific nanoparticle-cation bridging interaction, which is sensitive to the nanoparticle surface curvature. Increased apparent dissociation constant of carboxyl groups on the zero-curvature nanoplates' surface enhances bridging interactions and makes nanoplates colloidally unstable. Bridging interactions can be eliminated by using mixed bimolecular 11-mercaptoundecanoate-11-mercaptoundecanol surface ligand layer. Silver nanoplates with mixed ligand layer show an enhanced colloidal stability at a standard carbodiimide bioconjugation protocol.

Pseudo-refractive index and excitonic features of single layer CdSe/CdS core-shell nanoplatelet films.

Semiconductor CdSe/CdS core-shell nanoplatelets exhibit narrow and intense absorption and photoluminescence spectra in the visible range, which makes them suitable for numerous applications in optoelectronics. Of particular interest is the preparation and optical characterization of thin films with an accurately controlled amount of nanoplatelets. Here we report on the use of spectroscopic ellipsometry for investigating the optical properties of ultrathin films composed of a single layer of negatively charged CdSe/CdS core-shell nanoplatelets prepared by the electrostatic layer-by-layer deposition on SiO2/Si substrates. Combining the ellipsometric spectra with atomic force microscopy measurements, we were able to infer the nanoplatelet film extinction spectra which was found to exhibit the two characteristic exciton peaks albeit blueshifted relative to the colloidal nanoplatelets.

Emitters with different dimensionality: 2D cadmium chalcogenide nanoplatelets and 0D quantum dots in non-specific cell labeling and two-photon imaging.

Since CdSe nanoplatelets were reported to have a ten-fold higher two-photon (2P) absorption coefficient as compared to quantum dots, we examined their applicability for cell labeling and 2P imaging. CdSSe/ZnCdS core-shell nanoplatelets and CdSe/ZnS quantum dots, both emitting at 585 nm were encapsulated with an amphiphilic zwitterionic polymer having slightly positive zeta potential. As measured with flow cytometry, glioma C6 cells demonstrated equally efficient uptake of nanoplatelets and quantum dots, despite the different sizes of these two types of nanoparticles. 2P fluorescence microscopy revealed ca. two orders of magnitude higher fluorescence response from nanoplatelets thus offering a chance to use them as highly efficient 2P fluorescent labels in biomedicine.

Highly luminescent Zn-Cu-In-S/ZnS core/gradient shell quantum dots prepared from indium sulfide by cation exchange for cell labeling and polymer composites.

Gradient core-shell Zn-Cu-In-S/ZnS quantum dots (QDs) of small size and with highly efficient photoluminescence were synthesized via a multi-step high-temperature method involving cation exchange. The procedure starts with the preparation of indium sulfide nanoparticles followed by the addition of Cu and Zn precursors. At this stage, Zn replaces Cu atoms and as a result the concentration of Cu ions in the final QDs is only about 5% of the total In content in a QD. Zn incorporation and the formation of a gradient ZnS shell dramatically increases the photoluminescence quantum yield. Furthermore, the formation of the ZnS shell improves the chemical stability of Cu-In-S QDs, as demonstrated by the preparation of polystyrene-QD composites and labeling of glioma cells. This work provides an effective strategy for obtaining efficient and stable fluorophores free of heavy metals.

Colloidal branched CdSe/CdS 'nanospiders' with 2D/1D heterostructure.

In this paper we report the synthesis of colloidal CdSe/CdS core-shell heteronanoplatelets with epitaxially grown wurtzite (WZ) 1D CdS branches or legs by using cadmium diethyldithiocarbamate as a single-source precursor. The growth of WZ branches was achieved by exploiting zinc blende-wurtzite polytypism of cadmium chalcogenides induced by oleylamine. Synthesized 'nanospiders' exhibit enhanced absorption in the UV-blue region and narrow and relatively intense red photoluminescence depending on the amount of CdS in the heteronanostructure.

Directed Two-Photon Absorption in CdSe Nanoplatelets Revealed by k-Space Spectroscopy.

We show that two-photon absorption (TPA) is highly anisotropic in CdSe nanoplatelets, thus promoting them as a new class of directional two-photon absorbers with large cross sections. Comparing two-dimensional k-space spectroscopic measurements of the one-photon and two-photon excitation of an oriented monolayer of platelets, it is revealed that TPA into the continuum is a directional phenomenon. This is in contrast to one-photon absorption. The observed directional TPA is shown to be related to fundamental band anisotropies of zincblende CdSe and the ultrastrong anisotropic confinement. We recover the internal transition dipole distribution and find that this directionality arises from the intrinsic directionality of the underlying Bloch and envelope functions of the states involved. We note that the photoemission from the CdSe platelets is highly anisotropic following either one- or two-photon excitation. Given the directionality and high TPA cross-section of these platelets, they may, for example, find employment as efficient logic AND elements in integrated photonic devices, or directional photon converters.

Time-Resolved Stark Spectroscopy in CdSe Nanoplatelets: Exciton Binding Energy, Polarizability, and Field-Dependent Radiative Rates.

We present a study of the application potential of CdSe nanoplatelets (NPLs), a model system for colloidal 2D materials, as field-controlled emitters. We demonstrate that their emission can be changed by 28% upon application of electrical fields up to 175 kV/cm, a very high modulation depth for field-controlled nanoemitters. From our experimental results we estimate the exciton binding energy in 5.5 monolayer CdSe nanoplatelets to be EB = 170 meV; hence CdSe NPLs exhibit highly robust excitons which are stable even at room temperature. This opens up the possibility to tune the emission and recombination dynamics efficiently by external fields. Our analysis further allows a quantitative discrimination of spectral changes of the emission energy and changes in PL intensity related to broadening of the emission line width as well as changes in the intrinsic radiative rates which are directly connected to the measured changes in the PL decay dynamics. With the developed field-dependent population model treating all occurring field-dependent effects in a global analysis, we are able to quantify, e.g., the ground state exciton transition dipole moment (3.0 × 10-29 Cm) and its polarizability, which determine the radiative rate, as well as the (static) exciton polarizability (8.6 × 10-8 eV cm2/kV2), all in good agreement with theory. Our results show that an efficient field control over the exciton recombination dynamics, emission line width, and emission energy in these nanoparticles is feasible and opens up application potential as field-controlled emitters.

p-State Luminescence in CdSe Nanoplatelets: Role of Lateral Confinement and a Longitudinal Optical Phonon Bottleneck.

We evidence excited state emission from p states well below ground state saturation in CdSe nanoplatelets. Size-dependent exciton ground and excited state energies and population dynamics are determined by four independent methods: time-resolved PL, time-integrated PL, rate equation modeling, and Hartree renormalized k·p calculations-all in very good agreement. The ground state-excited state energy spacing strongly increases with the lateral platelet quantization. Depending on its detuning to the LO phonon energy, the PL decay of CdSe platelets is governed by a size tunable LO phonon bottleneck, related to the low exciton-phonon coupling, very large oscillator strength, and energy spacing of both states. This is, for instance, ideal to tune lasing properties. CdSe platelets are perfectly suited to control the exciton-phonon interaction by changing their lateral size while the optical transition energy is determined by their thickness.

Determination of Concentration of Amphiphilic Polymer Molecules on the Surface of Encapsulated Semiconductor Nanocrystals.

We present a method for the determination of the average number of polymer molecules on the surface of A(II)B(VI) luminescent core-shell nanocrystals (CdSe/ZnS, ZnSe/ZnS quantum dots, and CdS/ZnS nanorods) encapsulated with amphiphilic polymer. Poly(maleic anhydride-alt-1-tetradecene) (PMAT) was quantitatively labeled with amino-derivative of fluorescein and the average amount of PMAT molecules per single nanocrystal was determined using optical absorption of the dye in the visible spectral range. The average amount of PMAT molecules grows linearly with the surface area of all studied nanocrystals. However, the surface density of the monomer units increases nonlinearly with the surface area, because of the increased competition between PMAT molecules for Zn-hexanethiol surface binding sites. The average value of zeta potential (ζ = -35 mV) was found to be independent of the size, shape, and chemical composition of nanocrystals at fixed buffer parameters (carbonate-bicarbonate buffer, pH 9.5 and 5 mM ionic strength). This finding is expected to be useful for the determination of the surface density of remaining carboxyl groups in PMAT-encapsulated nanocrystals.

Temperature dependent radiative and non-radiative recombination dynamics in CdSe-CdTe and CdTe-CdSe type II hetero nanoplatelets.

We investigate the temperature-dependent decay kinetics of type II CdSe-CdTe and CdTe-CdSe core-lateral shell nanoplatelets. From a kinetic analysis of the photoluminescence (PL) decay and a measurement of the temperature dependent quantum yield we deduce the temperature dependence of the non-radiative and radiative lifetimes of hetero nanoplates. In line with the predictions of the giant oscillator strength effect in 2D we observe a strong increase of the radiative lifetime with temperature. This is attributed to an increase of the homogeneous transition linewidth with temperature. Comparing core only and hetero platelets we observe a significant prolongation of the radiative lifetime in type II platelets by two orders in magnitude while the quantum yield is barely affected. In a careful analysis of the PL decay transients we compare different recombination models, including electron hole pairs and exciton decay, being relevant for the applicability of those structures in photonic applications like solar cells or lasers. We conclude that the observed biexponential PL decay behavior in hetero platelets is predominately due to spatially indirect excitons being present at the hetero junction and not ionized e-h pair recombination.

Two Photon Absorption in II-VI Semiconductors: The Influence of Dimensionality and Size.

We report a comprehensive study on the two-photon absorption cross sections of colloidal CdSe nanoplatelets, -rods, and -dots of different sizes by the means of z-scan and two-photon excitation spectroscopy. Platelets combine large particle volumes with ultra strong confinement. In contrast to weakly confined nanocrystals, the TPA cross sections of CdSe nanoplatelets scale superlinearly with volume (V(∼2)) and show ten times more efficient two-photon absorption than nanorods or dots. This unexpectedly strong shape dependence goes well beyond the effect of local fields. The larger the particles' aspect ratio, the greater is the confinement related electronic contribution to the increased two-photon absorption. Both electronic confinement and local field effects favor the platelets and make them unique two-photon absorbers with outstanding cross sections of up to 10(7) GM, the largest ever reported for (colloidal) semiconductor nanocrystals and ideally suited for two-photon imaging and nonlinear optoelectronics. The obtained results are confirmed by two independent techniques as well as a new self-referencing method.

Methods and challenges for the practical application of Crit-Line™ monitor utilization in patients on hemodialysis.

The Crit-Line™ monitor measures relative changes in intravascular blood volume during hemodialysis. The device is also used to monitor hematocrit and oxygen saturation. Using this device to decrease fluid volume has yielded inconsistent results on outcome measures such as hospitalization rates, erythropoietin utilization, and blood pressure reduction. Through a year-long deployment of the Crit-Line™ monitor, the Renal Research Institute (RRI) has shown that outcomes can be improved even in a busy dialysis clinic with attention to the details of how the device is utilized. In this paper, we are proposing areas of focus and methods that if properly implemented should yield improved clinical outcomes. Strong physician approval and enthusiasm coupled with clinical staff support have been shown to be vital to the success of this device in improving clinical outcomes. Even in this setting, inadequately and improperly trained staff have been identified as almost insurmountable impediments to adequate Crit-Line™ use. Our studies have shown that in facilities where staff turnover is high, procedures must be implemented to engage and train new staff immediately upon their arrival on the dialysis floor. Other issues that may lead to improper use of the Crit-Line™ monitor include incorrect target weight assessments, failure of staff to properly monitor patients during the treatment, and the over dependency of saline administration for cramps.

CdSe-CdS nanoheteroplatelets with efficient photoexcitation of central CdSe region through epitaxially grown CdS wings.

We synthesized a new type of optically active semiconductor nanoheterostructure based on CdSe nanoplatelets with epitaxially grown CdS flat branches or wings. CdS branches work as efficient photonic antenna in the blue spectral region, enhancing the excitation of CdSe band edge emission. The formation of CdSe-CdS nanoheteroplatelets instead of CdSe/CdS core-shell nanoplatelets was achieved using short-chain Cd ethylhexanoate and sulfur in octadecene as precursors for CdS overgrowth in the presence of acetate salt.

Anisotropy of optical transitions in ordered ensemble of CdSe quantum rods.

We report on the observation of spectral dependence of absorption anisotropy in a CdSe quantum rod (QR) ensemble, which is aligned in a polymer film with a nanocrystal concentration of 2×10(-5) M. The experimental data on the polarization direction and anisotropy factor were obtained for the lowest excitonic transition and the second group of transitions in the QR. The nonzero constant value of anisotropy was investigated for the high-energy transitions, and is evidence of the one-dimensional confinement in the QR.

Basic principles and current trends in colloidal synthesis of highly luminescent semiconductor nanocrystals.

The principal methods for the synthesis of highly luminescent core-shell colloidal quantum dots (QDs) of the most widely used CdSe, CdS, ZnSe, and other A(II) B(VI) nanocrystals are reviewed. One-pot versus multistage core synthesis approaches are discussed. The noninjection one-pot method ensures slow, controllable growth of core nanocrystals starting from magic-size seed recrystallization, which yields defect-free cores with strictly specified sizes and shapes and a high monodispersity. Subsequent injection of shell precursors allows the formation of gradient core-shell QDs with a smooth potential barrier for electrons and holes, without strains or interfacial defects, and, as a consequence, a luminescence quantum yield (QY) approaching 100%. These general approaches can also be applied to semiconductor core-shell QDs other than A(II) B(VI) ones to cover the broad spectral range from the near-UV to IR regions of the optical spectrum, thus displacing fluorescent organic dyes from their application areas.

Electronic structure and exciton-phonon interaction in two-dimensional colloidal CdSe nanosheets.

We study the electronic structure of ultrathin zinc-blende two-dimensional (2D)-CdSe nanosheets both theoretically, by Hartree-renormalized k·p calculations including Coulomb interaction, and experimentally, by temperature-dependent and time-resolved photoluminescence measurements. The observed 2D-heavy hole exciton states show a strong influence of vertical confinement and dielectric screening. A very weak coupling to phonons results in a low phonon-contribution to the homogeneous line-broadening. The 2D-nanosheets exhibit much narrower ensemble absorption and emission linewidths as compared to the best colloidal CdSe nanocrystallites ensembles. Since those nanoplatelets can be easily stacked and tend to roll up as they are large, we see a way to form new types of multiple quantum wells and II-VI nanotubes, for example, for fluorescence markers.

Multiple underlying images tuned by Mn-doped Zn-Cu-In-S quantum dots.

In this study, ZnS capped Cu-In-S (ZCIS) quantum dots doped with Mn ions are synthesized by a thermal injection method, with luminescence covering almost the entire visible area. The large Stokes shift effectively inhibits the self-absorption effect under luminescence, and the quantum yield of ZCIS quantum dots increased from 38% to 50% after ZnS capping and further to 69% after doping with Mn. First, red-, yellow-, and blue-emitting quantum dots were synthesized and then, polychromatic ensembles were obtained by mixing the trichromatic quantum dots in a different ratio. Using the home-built inkjet printer, multilayered and multicolor mixed patterns were obtained for information pattern storage and multilayer pattern recognition and reading.

Spatio-temporally deciphering peripheral nerve regeneration in vivo after extracellular vesicle therapy under NIR-II fluorescence imaging.

Extracellular vesicles (EVs) show potential as a therapeutic tool for peripheral nerve injury (PNI), promoting neurological regeneration. However, there are limited data on the in vivo spatio-temporal trafficking and biodistribution of EVs. In this study, we introduce a new non-invasive near-infrared fluorescence imaging strategy based on glucose-conjugated quantum dot (QDs-Glu) labeling to target and track EVs in a sciatic nerve injury rat model in real-time. Our results demonstrate that the injected EVs migrated from the uninjured site to the injured site of the nerve, with an increase in fluorescence signals detected from 4 to 7 days post-injection, indicating the release of contents from the EVs with therapeutic effects. Immunofluorescence and behavioral tests revealed that the EV therapy promoted nerve regeneration and functional recovery at 28 days post-injection. We also found a relationship between functional recovery and the NIR-II fluorescence intensity change pattern, providing novel evidence for the therapeutic effects of EV therapy using real-time NIR-II imaging at the live animal level. This approach initiates a new path for monitoring EVs in treating PNI under in vivo NIR-II imaging, enhancing our understanding of the efficacy of EV therapy on peripheral nerve regeneration and its mechanisms.

Comparative efficiency of energy transfer from CdSe-ZnS quantum dots or nanorods to organic dye molecules.

Fluorescence resonance energy transfer (FRET) in conjugates of CdSe-ZnS semiconductor nanocrystals of different shapes (FRET donors) and an Alexa Fluor organic dye (FRET acceptors) is examined. The dye molecules are chemically conjugated with quantum dots (QDs) or nanorods (NRs) in dimethyl sulfoxide colloidal solutions, and FRET efficiency in the purified conjugates is measured. The FRET from NR to a single dye molecule is less efficient than that of the QD-dye conjugates and this effect is explained in terms of distance-limited energy-transfer rate in the case of a point-like acceptor and extended donor dipoles. However, the larger surface area of NRs allows for many more dye acceptors to be bound, and the total FRET efficiency in NR-dye conjugates approaches those of QD-dye conjugates.

Oriented conjugates of single-domain antibodies and quantum dots: toward a new generation of ultrasmall diagnostic nanoprobes.

Common strategy for diagnostics with quantum dots (QDs) utilizes the specificity of monoclonal antibodies (mAbs) for targeting. However QD-mAbs conjugates are not always well-suited for this purpose because of their large size. Here, we engineered ultrasmall nanoprobes through oriented conjugation of QDs with 13-kDa single-domain antibodies (sdAbs) derived from llama IgG. Monomeric sdAbs are 12 times smaller than mAbs and demonstrate excellent capacity for refolding. sdAbs were tagged with QDs through an additional cysteine residue integrated within the C terminal of the sdAb. This approach allowed us to develop sdAbs-QD nanoprobes comprising four copies of sdAbs coupled with a QD in a highly oriented manner. sdAbs-QD conjugates specific to carcinoembryonic antigen (CEA) demonstrated excellent specificity of flow cytometry quantitative discrimination of CEA-positive and CEA-negative tumor cells. Moreover, the immunohistochemical labeling of biopsy samples was found to be comparable or even superior to the quality obtained with gold standard protocols of anatomopathology practice. sdAbs-QD-oriented conjugates as developed represent a new generation of ultrasmall diagnostic probes for applications in high-throughput diagnostic platforms. FROM THE CLINICAL EDITOR: The authors report the development of sdAbs-QD-oriented conjugates, comprised of single domain antibodies that are 12 times smaller than regular mAb-s and quantum dots. These ultrasmall diagnostic probes represent a new generation of functionalized ODs for applications in high-throughput diagnostic platforms.